Catalysts based on mixed Cu-Co oxides (CuCo2O4 spinel) supported over a dealuminized metakaolinite were synthesized and evaluated in the glycerol oxidation reaction. Parameters such as temperature reaction (60 °C and 80 °C), glycerol:H2O2 molar ratio (1:2 and 1:4), and reaction time (2h and 4h) were investigated. The best catalytic results were obtained at 80 °C and a 1:2 glycerol:H2O2 molar ratio, with a glycerol conversion of 70.6% and selectivity to dihydroxyacetone of 88% after 4h of reaction. Nevertheless, to improve the stability, the catalyst was calcined at 400 °C, 600 °C and 800 °C. The catalyst calcined at 800 °C had superior catalytic performance with 77% glycerol conversion at half the time (2h), indicating a favorable catalytic effect related to an increase in the crystallinity of the spinel particles and a possible increase in their dispersion. Additionally, this catalyst was the most stable almost during 4 reaction cycles.